Catalyst composition for preparing olefin polymers

ABSTRACT

A catalyst composition for preparing olefin polymers. The catalyst composition includes a metallocene compound and an activating cocatalyst. In the metallocene compound, two cyclopentadienyl groups are bridged by X (carbon, silicon, germanium or tin) in a ring structure. The bite angle θ formed by the two cyclopentadienyl rings and X is equal to or greater than 100 degrees. The obtained olefin polymer has high cycloolefin conversion and a high glass transition temperature. In addition, the catalyst composition can still maintain relatively high activity at high temperature reaction conditions.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of application Ser. No. 10/244,435,filed Sep. 17, 2000, now U.S. Pat. No. 6,875,719 the disclosure of whichis incorporated herein by reference, and which is a continuation-in-partof application Ser. No. 09/559,976, filed on Apr. 27, 2000, nowabandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a catalyst composition for preparingolefin polymers, and more particularly to a catalyst composition forpreparing cycloolefin copolymers with a high cycloolefin conversion anda high glass transition temperature. The catalyst composition can stillmaintain relatively high activity at high temperature reactionconditions.

2. Description of the Prior Art

Olefin-based polymers have been used in a wide range of applications.One group of commonly used olefin-based polymers is polyolefins, thatis, homopolymers or copolymers of olefins. These polyolefin polymers aretypically used in such applications as blow and injection molding,extrusion coating, film and sheeting, pipe, wire and cable.

An example of polyolefin is ethylene-propylene elastomer(ethylene-propylene rubbers, EPR). It has many end-use applications dueto its resistance to weather, good heat aging properties and its abilityto be compounded with large quantities of fillers and plasticizers.Typical automotive uses are radiator and heater hoses, vacuum tubing,weather stripping and sponge doorseals. Typical industrial uses aresponge parts, gaskets and seals.

Another group of commonly used olefin-based polymers is cycloolefincopolymers (COC). One of the examples is a copolymer of cycloolefin andethylene, which has an extraordinarily high glass transition temperaturecompared with traditional polyolefins owing to its incorporation ofcyclic monomers. Also, the polymer has high transparency in physicalproperties due to reduced crystallinity by the incorporation of cyclicmonomers. The combination of light transparency, heat resistance, agingresistance, chemical resistance, solvent resistance, and low dielectricconstant makes COC a valuable material that has attracted researchactivities in both academic and industrial sectors. Currently,ethylene/cycloolefin copolymers have been demonstrated to be a suitablematerial in the field of optical materials such as optical memory disksand optical fibers.

Ethylene/cycloolefin copolymers are usually prepared in the presence ofmetallocene/aluminoxane catalyst systems, as described in U.S. Pat. No.5,559,199 (Abe et al.) and U.S. Pat. No. 5,602,219 (Aulbach et al.) InU.S. Pat. No. 5,559,199, metallocenes such as isopropylidene(cyclopentadienylmethylcyclopentadienyl)zirconium dichloride aredisclosed. In U.S. Pat. No. 5,602,219, metallocenes such asdimethylsilyl-(1-indenyl)-cyclopentadienylzirconium dichloride aredisclosed.

However, conventional processes for preparing ethylene-cycloolefincopolymers have some common problems. First, the conversion of thecycloolefin (or the incorporation of the cycloolefin) is too low.Second, the high incorporation of ethylene results in too low a glasstransition temperature (Tg) of the copolymer.

To increase the conversion of the cycloolefin, a common technique is toincrease the reaction temperature or reducing reaction pressure ofethylene. However, using this technique, the reactivity for theproduction of cycloolefin polymer will be reduced as the examples showin U.S. Pat. Nos. 5,602,219 and 5,559,199. Obviously, this techniquewill reduce the commercial feasibility for COC polymerization.Therefore, efforts to enhance the reactivity of catalyst for increasingthe incorporation of cyclic olefins during the COC polymerizationprocesses are highly desirable in the industrial applications.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a catalyst compositionfor preparing olefin polymers, particularly for preparingethylene/cycloolefin copolymers with high cycloolefin incorporation anda high Tg.

To achieve the above-mentioned object, the catalyst composition of thepresent invention catalyst composition for preparing an olefin polymerincludes (a) a metallocene compound represented by formula (I) and (b)an activating cocatalyst.

Formula (I) has the structure

wherein

R¹ can be the same or different and is hydrogen, halogen, an alkyl,alkenyl, aryl, alkylaryl or arylalkyl group having from 1 to 20 carbonatoms, or two adjacent R¹ groups can link together with the carbon atomsto which they are attached to form a saturated or unsaturated ringsystem having from 4 to 20 carbon atoms;

R² can be the same or different and has the same definition as R¹;

X is carbon, silicon, germanium or tin;

n is 2 to 12;

R³ and R⁴ can be the same or different and are hydrogen, halogen, analkyl, alkenyl, aryl, alkylaryl or arylalkyl group having from 1 to 12carbon atoms;

M is a Group IVB transition metal with an oxidation state of +4;

Y is the same or different and is independently an anionic ligand with a−1 valence; and

the angle θ formed by the two cyclopentadienyl rings and X is equal toor greater than 100 degrees.

In formula (I), X is preferably carbon or silicon, and n is preferably2, 3 or 4.

The activating cocatalyst can be (1) an aluminoxane, (2) a mixture ofAlR¹¹R¹²R¹³ and a borate, or (3) a mixture of AlR¹¹R¹²R¹³ and analuminoxane, wherein R¹¹, R¹², and R¹³ are a C₁₋₂₀ aliphatic group or aC₆₋₁₀ aromatic group.

The catalyst composition of the present invention can be used to preparean olefin polymer. Using the catalyst composition to prepare acycloolefin copolymer, the cycloolefin incorporation is increased, andthe copolymer obtained has a high glass transition temperature rangingfrom 60° C.-350° C.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an X-ray crystal structure of the metallocene compoundprepared from Catalyst Example 5 of the present invention.

FIG. 2 is an X-ray crystal structure of the metallocene compoundprepared from Catalyst Example 6 of the present invention.

FIG. 3 is an X-ray crystal structure of the metallocene compoundprepared from Catalyst Example 7 of the present invention.

FIG. 4 is an X-ray crystal structure of the metallocene compoundprepared from Comparative Catalyst Example 8 of the present invention.

FIG. 5 is an X-ray crystal structure of the metallocene compoundprepared from Comparative Catalyst Example 9 of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a catalyst composition for preparingolefin polymers, which includes a metallocene compound represented byformula (I) and an activating cocatalyst.

One aspect of the present invention resides in that X (Group IVA elementsuch as C) in formula (I) is bridged by —(CR³R⁴)_(n)— to form a three-,four-, or five-member ring structure, wherein n is 2, 3 or 4. Thus, theangle θ formed by the two cyclopentadienyl rings and X is equal to orgreater than 100 degrees.

Referring to the conventional metallocenes for preparing cycloolefincopolymers in U.S. Pat. No. 5,559,199 (U.S. Pat. No. '199) and U.S. Pat.No. 5,602,219 (U.S. Pat. No. '219) as mentioned above, for example,isopropylidene(cyclopenta-dienylfluorenyl)zirconium dichloride anddimethylsilyl-(1-indenyl)cyclopentadienylzirconium dichloride, it can beseen that two methyl groups are bonded to the carbon or silicon atom ofthe metallocene. Part of the chemical structure of the metallocene isdepicted in the Table 1 for better understanding, in which Cp indicatesunsubstituted or substituted cyclopentadienyl, and θ₁, θ₂, and θ₃,indicate the angle formed by Cp, Group IVA element, and another Cp(Cp-IVA-Cp), which is called the bite angle.

TABLE 1 U.S. ′199 (bite U.S. ′219 (bite Present invention angle's X-raydata, angle's X-ray data, (bite angle, see Journal of see Organometallicsee FIG. 1 and Organometallic 1994, 13, 964 and Table 2) vide infraChemistry Journal of 1995, 497, 105). Organometallic Chemistry 1989,369, 359).

In contrast with the metallocene of U.S. Pat. No. '199 and U.S. Pat. No.'219, the Group IVA element such as carbon is bridged by —(CR³R⁴)_(n)—(n=2, 3 or 4) to form a ring structure in the present invention. As aresult of this bridging, the angle formed by Cp-IVA-Cp can be enlarged.That is to say, angle θ₃ is larger than both θ₁ and θ₂. It should benoted that to date, metallocene catalysts containing a bite angle largerthan 100 degrees have never been reported from prior art.

When a conventional metallocene compound is used as a catalyst toprepare a copolymer of a cycloolefin and an acyclic olefin (such asethylene), since the bite angle is is small, it is difficult for thecycloolefin that has a larger size than ethylene to approach themetallocene's active site. Thus, an undesired low incorporation amountof the cycloolefin occurs in the copolymer produced. However, when themetallocene compound of the present invention is used as the catalyst,the larger bite angle leads to a greater vacancy around themetallocene's active site. Thereby the larger sized cycloolefin hasgreater probability to approach the reactive site. Consequently,copolymers produced using the catalyst composition of the presentinvention tend to have a higher cycloolefin incorporation in the polymerbackbone, thus significantly increasing their glass transitiontemperatures (Tg).

The scientific basis is explained as follows. In a bridged metalloceneof the present invention, when the bite angle between two Cp rings opensup, the active center of the metal moves outward. This willsubstantially increase the ratio of the coordination speed of acycloolefin to acyclic olefin monomer with the active center of thecatalyst compared with other catalysts, which increases the ratio of thecycloolefin relative to acyclic olefin monomer incorporated in theresulting copolymer in turn. The Tg of the copolymer increasesaccordingly, and the polymerization activity also increases. It shouldbe noted that in a bridged metallocene catalyst, the bite angleresulting from a carbon bridge is obviously larger than that from asilicon bridge. One reason is that the element radius of carbon (0.77 Å)is smaller than that of silicon (1.11 Å). The other reason is that theelectronegativity of carbon (2.5) is larger than that of silicon (1.8),thus carbon-carbon has a far larger bonding energy than silicon-carbon.Therefore, when Cp is bridged with a group IVA element, the siliconbridge has a larger degree of deformation than carbon, resulting in asmaller bite angle.

In formula (I), when R¹ and R² are an alkyl, alkenyl, aryl, alkylaryl orarylalkyl group having from 1 to 20 carbon atoms, preferably from 1 to15 carbon atoms, they are preferably C₁₋₁₀ alkyl, C₁₋₁₀ alkenyl, C₆₋₁₀aryl, C₇₋₁₀ alkylaryl, and C₇₋₁₀ arylalkyl. Representative examples ofR¹ and R² include H, methyl, ethyl, propyl, butyl, isobutyl, amyl,isoamyl, hexyl, 2-ethylhexyl, heptyl, octyl, vinyl, allyl, isopropenyl,phenyl, and tolyl.

When two adjacent R¹ (or R²) groups link together with the carbon atomsto which they are attached to form a ring system having from 4 to 20carbon atoms, preferably 4 to 6 carbon atoms, R¹ (or R²) can form withthe cyclopentadienyl moiety to which they are attached a saturated orunsaturated polycyclic cyclopentadienyl ring such as an indenyl,tetrahydroindenyl, fluorenyl or octahydrofluorenyl group. Representativeexamples of such rings include η⁵-cyclopentadienyl,η⁵-methylcyclopentadienyl, η⁵-ethylcyclopentadienyl,η⁵-propylcyclopentadienyl, η⁵-tetramethylcyclopentadienyl,η⁵-pentamethylcyclopentadienyl, η⁵-n-butylcyclopenta-dienyl, indenyl,tetrahydroindenyl, fluorenyl, and octahydrofluorenyl.

Y can be H, a C₁₋₂₀ hydrocarbon group, a halogen, C₆₋₂₀ aryl, C₇₋₂₀alkylaryl or arylalkyl, C₁₋₂₀ alkoxy, C₁₋₂₀ aryloxy, NH₂, NHR⁷, NR⁷R⁸,—(C═O)NH₂, —(C═O)NHR⁹, —(C═O)NR⁹R¹⁰, each of R⁷, R⁸, R⁹ and R¹⁰ beingC₁₋₂₀ hydrocarbyl. Suitable Y groups include methyl, ethyl, phenyl,chlorine, bromine, methoxy, ethoxy, —NH₂, —NH(CH₃), —N(CH₃)₂, —N(C₂H₅)₂,and —N(C₃H₇)₂.

In the present invention, the metallocene compound represented byformula (I) can be combined with an activating coatalyst to form acatalyst composition, which can be used for preparing olefin polymers.

The cocatalyst used in the present invention can be (1) an aluminoxane,(2) a mixture of AlR¹¹R¹²R¹³ and a borate, or (3) a mixture ofAlR¹¹R¹²R¹³ and an alumoxane. R¹¹, R¹², and R¹³ are a C₁₋₂₀ aliphaticgroup or a C₆₋₁₀ aromatic group. A preferred aluminoxane is methylaluminoxane. Representative examples of AlR¹¹R¹²R¹³ include trimethylaluminum, triethyl aluminum, tripropyl aluminum, trisopropyl aluminum,tributyl aluminum, and triisobutyl aluminum (TIBA). Representativeexamples of borates include N,N-dimethyl aniliniumtetrakis(pentafluorophenyl)borate, triphenyl carbeniumtetrakis(pentafluorophenyl)borate, trimethyl ammoniumtetrakis(pentafluorophenyl)borate, ferroceniumtetrakis(pentafluorophenyl)borate, dimethyl ferroceniumtetrakis(pentafluorophenyl)borate, and silvertetrakis(pentafluorophenyl)borate.

Using the catalyst composition of the present invention, an olefinpolymer can be synthesized. In the presence of a catalytically effectiveamount of the catalyst composition of the present invention underpolymerizing conditions, an olefin monomer can be subjected topolymerization (homopolymerization), or at least one olefin monomertogether with at least one other monomer can be subjected topolymerization (copolymerization).

According to the present invention, a preferred olefin is a cycloolefin.Preferably, the polymerization of the present invention ishomopolymerization of a cycloolefin, or copolymerization of acycloolefin and an acycloolefin.

Cycloolefins suitable for use in the present invention include abicycloheptene, a tricyclodecene, a tricycloundecene, atetracyclododecene, a pentacyclopentadecene, a pentacyclopentadecadiene,a pentacyclohexadecene, a hexacycloheptadecene, a heptacycloeicosene, aheptacycloheneicosene, an octacyclodocosene, a nonacyclopentacosene, anda nonacyclohexacosene. Representative examples include norbornene,tetracyclododecene, dicyclopentadiene, and ethylidene norbornene.

Suitable acyclic olefins can be ethylene or α-olefins. Representativeexamples of α-olefins include those olefins having 3 to 12 carbon atoms,such as propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene.

More particularly, the catalyst composition of the present invention canbe advantageously used to prepare acylic olefin/cycloolefin copolymers,such as ethylene/cycloolefin copolymers. By means of the specificcatalyst composition, the ethylene/cycloolefin copolymer obtained willhave a high cycloolefin conversion and a high Tg.

By means of the specific catalyst composition of the present invention,the resulting olefin polymer has a glass transition temperature rangingfrom 60-350° C., preferably 120-350° C., most preferably 250-350° C.

The novel catalyst composition disclosed in the present invention can beused in slurry reactions, gas phase reactions, and solutionpolymerization reactions. According to the experimental results of thepresent invention, it can be proved that the specific catalystcomposition of the present invention can still have superior activity ata higher reaction temperature. Such superior activity will lead to theincrease of the cycloolefin incorporation amount, and the cycloolefincopolymer obtained will have an increased Tg, which can not be achievedby a conventional similar catalyst.

According to the present invention, representative examples of themetallocene compound of formula (I) include the following formulae:

wherein R is a C₁-C₂₀ hydrocarbyl group,

wherein R is a C₁-C₂₀ hydrocarbyl group,

wherein R is a C₁-C₂₀ hydrocarbyl group,

wherein A is halogen,

wherein R is a C₁-C₂₀ hydrocarbyl group,

wherein R is a C₁₋₂₀ hydrocarbyl group,

wherein A is halogen, and

wherein A is halogen.

The following examples are intended to illustrate the process and theadvantages of the present invention more fully without limiting itsscope, since numerous modifications and variations will be apparent tothose skilled in the art. Unless otherwise indicated, all parts,percents, ratios and the like are by weight.

Synthesis of Metallocene CATALYST EXAMPLE 1 Synthesis of1-cyclopentadienyl-1-indenylcyclobutane (a bridged cyclopentadiene)

Indene (5.8 g, 50 mmole) was placed in a 250 ml round bottom flask with50 ml of THF (tetrahydrofuran). 40 ml (1.6 M, 64 mmole) of n-butyllithium (n-BuLi) was is added into the solution under an ice bath. Themixture turned orange red. The ice bath was removed and the mixture wasstirred for 3 hours. Then, the reaction mixture was stripped undervacuum to remove solvent, washed with 50 ml of pentane to remove excessn-BuLi, and filtered to collect the precipitate.

The precipitate was dissolved in 50 ml of THF and6,6-trimethylenefulvene (5.9 g, 50 mmole) was added gradually to thesolution under an ice bath. After stirring for 24 hours, 1 ml of waterwas added to the mixture to terminate the reaction. The reaction mixturewas stripped under vacuum to remove solvent, dissolved with 100 ml ofhexane, and filtered to collect the filtrate. The crude product (i.e.,filtrate) was purified by column chromatography (the packing was 20 g ofsilica gel, the eluent was 100% hexane). The solution was thenconcentrated under reduced pressure to obtain a pale yellow liquid (8.2g, yield=70%).

CATALYST EXAMPLE 2 Synthesis of1-methylcyclopentadienyl-1-indenyl-cyclobutane

Indene (2.9 g, 25 mmole) was placed in a 250 ml round bottom flask with30 ml of THF (tetrahydrofuran). 20 ml (1.6 M, 32 mmole) of n-butyllithium (n-BuLi) was added into the solution under an ice bath. Themixture turned orange red. The ice bath was removed and the mixture wasstirred for 3 hours. Then, the reaction mixture was stripped undervacuum to remove solvent, washed with 50 ml of pentane to remove excessn-BuLi, and filtered to collect the precipitate.

The precipitate was dissolved in 30 ml of THF and3-methyl-6,6-trimethylenefulvene (3.3 g, 25 mmole) was added graduallyto the solution under an ice bath. After stirring for 24 hours, 1 ml ofwater was added to the mixture to terminate the reaction. The reactionmixture was stripped under vacuum to remove solvent, dissolved with 50ml of hexane, and filtered to collect the filtrate. The crude product(i.e., filtrate) was purified by column chromatography (the packing was20 g of silica gel, the eluent was 100% hexane). The solution was thenconcentrated under reduced pressure to obtain a pale yellow liquid (4.7g, yield=75.8%).

CATALYST EXAMPLE 3 Synthesis ofcyclobutylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)bis(dimethylamino)zirconium

1-Cyclopentadienyl-1-indenylcyclobutane (0.94 g, 4 mmole) obtained as inCatalyst Example 1 and Zr(NMe₂)₄ (1 g, 3.7 mmole) were placed in a 100ml round bottle flask. 20 ml of toluene was added to the flask and themixture was allowed to react at room temperature for 15 hours. Thereaction mixture was stripped under vacuum to remove solvent and then 50ml of pentane was added to dissolve the residue. The solution wasfiltered and the filtrate was then concentrated to obtain a yellow solid(1.45 g, yield=95%).

CATALYST EXAMPLE 4 Synthesis ofcyclobutylidene(1-η⁵-methylcyclopentadienyl)(1-η⁵-indenyl)bis(dimethylamino)zirconium

1-Methylcyclopentadienyl-1-indenylcyclobutane (0.99 g, 4 mmole) obtainedas in Catalyst Example 2 and Zr(NMe₂)₄ (1 g, 3.7 mmole) were placed in a100 ml round bottle flask. 20 ml of toluene was added to the flask andthe mixture was allowed to react at room temperature for 15 hours. Thereaction mixture was stripped under vacuum to remove solvent and then 50ml of pentane was added to dissolve the residue. The solution wasfiltered and the filtrate was then concentrated to obtain a yellow solid(1.54 g, yield=98%).

CATALYST EXAMPLE 5 Synthesis ofcyclobutylidene(1-η⁵-cyclopentadienyl)(1-η⁵-fluorenyl)zirconiumdichloride

1-cyclopentadienyl-1-fluorenylcyclobutane was prepared by similarprocedures as described in Catalyst Example 1. The resulting substance(1.14 g, 4 mmole) was combined in toluene with Zr(NMe₂)₄ (1 g, 3.7mmole) within a 100 ml round bottle flask. 20 ml of toluene was added tothe flask and the mixture was allowed to react at room temperature for15 hours for providing the metallocene amide complex. The resultingsolution was then treated with 1.05 ml of trimethylsilylchloride. Theresulting solution was then allowed to react at room temerature for 6 hrto privide a yellow precipitate ofcyclobutylidene(1-η⁵-cyclopentadienyl)(1-η⁵-fluorenyl)zirconiumdichloride (1.15 g, 62% yield).

The precipitating powder of the catalyst was then recrystallized overtoluene to form an X-ray quality single crystalline catalyst. X-raycrystal data and structural refinement were recorded by a Nonius Kappaccd diffractometer at 295 K. Crystal data and structure refinement forthe product cyclobutylidene(1-η⁵-cyclopentadienyl)(1-η⁵-fluorenyl)zirconium dichloride (labeled to IC 8359) is shown inTable 2 attached. Selected bond lengths and bond angles are listed inTable 3 attached. X-ray crystal structure is shown in FIG. 1. Theresults clearly indicate that a novel catalyst with exceptional largebite angle (100.8°) was obtained in the system.

CATALYST EXAMPLE 6 Synthesis ofcyclobutylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)zirconium dichloride

(1) 6,6-trimethylenefulvene (Catalyst A)

5 g of cyclobutanone (71 mmol) and 14.35 ml of cyclopentadiene (175mmol) were charged in a 300 ml reaction bottle. 70 ml of CH₃OH was addedas a solvent. Then, 8.75 ml of pyrrolidine (105 mmol) was addedgradually and the mixture was stirred at room temperature for 30minutes. Next, 6.3 ml of CH₃COOH (105 mmol) was added gradually andstirred for 10 minutes. 200 ml of H₂O and 200 ml of pentane were usedfor extraction. The upper pentane portion was collected. The lower waterportion was further extracted with pentane three times. The collectedpentane portion was dehydrated with MgSO₄, held still for 30 minutes,filtered, and concentrated under reduced pressure to afford a yellowliquid product (5.5 g, yield=68.9%).

(2) 1-cyclopentadienyl-1-indenylcyclobutane

Indene (5.8 g, 50 mmole) was placed in a 250 ml round bottom flask with50 ml of THF (tetrahydrofuran). 34.3 ml (1.6 M, 55 mmole) of n-butyllithium (n-BuLi) was added into the solution under an ice bath. Themixture turned orange red. The ice bath was removed and the mixture wasstirred for 3 hours. 5.4 g of 6,6-trimethylenefulvene (46 mmole) wasadded gradually to the mixture. After stirring for 24 hours, 1 ml ofwater was added to the mixture to terminate the reaction. The reactionmixture was stripped under vacuum to remove solvent, washed with 100 mlof pentane, and filtered to remove the salt. The crude product (i.e.,filtrate) was purified by column chromatography (the packing was 20 g ofsilica gel, the eluent was 100% pentane). The solution was thenconcentrated under reduced pressure to obtain a pale yellow liquid (6.96g, yield=65%).

(3)cyclobutylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)bis(dimethylamino)zirconium

1 g of 1-Cyclopentadienyl-1-indenylcyclobutane (4.3 mmol) obtained andZr(NMe₂)₄ (1.06 g, 4.0 mmol) were placed in a 100 ml round bottle flask.50 ml of toluene was added to the flask and the mixture was allowed toreact for 24 hours. The reaction mixture was stripped under vacuum toremove solvent and then 20 ml of pentane was added to dissolve theresidue. The solution was filtered and the filtrate was thenconcentrated to obtain an orange yellow solid (1.47 g, yield=89.3%).

(4) cyclobutylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)-zirconiumdichloride

0.5 g ofcyclobutylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)bis(dimethylamino)zirconium(1.2 mmol) was charged in a 100 ml round bottle and 20 ml of toluene wasadded. 0.39 g of (CH₃)₃SiCl (3.6 mmol) was added gradually at roomtemperature and the mixture was allowed to react for 24 hours. Thereaction mixture stripped under vacuum to remove solvent and washed withpentane several times to remove excess (CH₃)₃SiCl. The pentane solutionwas then concentrated to obtain a pale yellow solid (0.4 g,yield=83.5%). X-ray crystal structure of the productcyclobutylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)-zirconiumdichloride is shown in FIG. 2. The results clearly indicate that a novelcatalyst with exceptional large bite angle (100.44°) was obtained in thesystem.

CATALYST EXAMPLE 7 Synthesis ofcyclopentylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)zirconiumdichloride (Catalyst B)

(1) 6,6-tetramethylenefulvene

6 g of cyclopentanone (71 mmol) and 14.35 ml of cyclopentadiene (175mmol) were charged in a 300 ml reaction bottle. 70 ml of CH₃OH was addedas a solvent. Then, 8.75 ml of pyrrolidine (105 mmol) was addedgradually and the mixture was stirred at room temperature for 30minutes. Next, 6.3 ml of CH₃COOH (105 mmol) was added gradually andstirred for 10 minutes. 200 ml of H₂O and 200 ml of pentane were usedfor extraction. The upper pentane portion was collected. The lower waterportion was further extracted with pentane three times. The collectedpentane portion was dehydrated with MgSO₄, held still for 30 minutes,filtered, and concentrated under reduced pressure to afford a yellowliquid product (8.4 g, yield=89%).

(2) 1-cyclopentadienyl-1-indenylcyclopentane

Indene (5.8 g, 50 mmole) was placed in a 250 ml round bottom flask with50 ml of THF (tetrahydrofuran). 34.3 ml (1.6 M, 55 mmole) of n-butyllithium (n-BuLi) was added into the solution under an ice bath. Themixture turned orange red. The ice bath was removed and the mixture wasstirred for 3 hours. 6.1 g of 6,6-tetramethylenefulvene (46 mmole) wasadded gradually to the mixture. After stirring for 24 hours, 1 ml ofwater was added to the mixture to terminate the reaction. The reactionmixture was stripped under vacuum to remove solvent, washed with 100 mlof pentane, and filtered to remove the salt. The crude product (i.e.,filtrate) was purified by column chromatography (the packing was 20 g ofsilica gel, the eluent was 100% pentane). The solution was thenconcentrated under reduced pressure to obtain a pale yellow liquid (7.6g, yield=67%).

(3)cyclopentylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)bis(dimethylamino)zirconium

1 g of 1-cyclopentadienyl-1-indenylcyclopentane (4.0 mmol) obtained andZr(NMe₂)₄ (0.96 g, 3.6 mmol) were placed in a 100 ml round bottle flask.50 ml of toluene was added to the flask and the mixture was allowed toreact for 24 hours. The reaction mixture was stripped under vacuum toremove solvent and then 20 ml of pentane was added to dissolve theresidue. The solution was filtered and the filtrate was thenconcentrated to obtain an orange yellow solid (1.41 g, yield=90.2%).

(4) cyclopentylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)-zirconiumdichloride

0.51 g, ofcyclopentylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)bis(dimethylamino)zirconium(1.2 mmol) was charged in a 100 ml round bottle and 20 ml of toluene wasadded. 0.39 g of (CH₃)₃SiCl (3.6 mmol) was added gradually at roomtemperature and the mixture was allowed to react for 24 hours. Thereaction mixture stripped under vacuum to remove solvent and washed withpentane several times to remove excess (CH₃)₃SiCl. The pentane solutionwas then concentrated to obtain a pale yellow solid (0.42 g,yield=85.7%). X-ray crystal structure of the productcyclopentylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)-zirconiumdichloride is shown in FIG. 3. The results clearly indicate that a novelcatalyst with exceptional large bite angle (101.0°) was obtained in thesystem.

COMPARATIVE CATALYST EXAMPLE 8 Synthesis ofcycloheptylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)zirconiumdichloride (Catalyst C)

(1) 6,6-hexamethylenefulvene

8 g, of cycloheptanone (71 mmol) and 14.35 ml of cyclopentadiene (175mmol) were charged in a 300 ml reaction bottle. 70 ml of CH₃OH was addedas a solvent. Then, 8.75 ml of pyrrolidine (105 mmol) was addedgradually and the mixture was stirred at room temperature for 30minutes. Next, 6.3 ml of CH₃COOH (105 mmol) was added gradually andstirred for 10 minutes. 200 ml of H₂O and 200 ml of pentane were usedfor extraction. The upper pentane portion was collected. The lower waterportion was further extracted with pentane three times. The collectedpentane portion was dehydrated with MgSO₄, held still for 30 minutes,filtered, and concentrated under reduced pressure to afford a yellowliquid product (10.6 g, yield=93%).

(2) 1-cyclopentadienyl-1-indenylcycloheptane

Indene (5.8 g, 50 mmole) was placed in a 250 ml round bottom flask with50 ml of THF (tetrahydrofuran). 34.3 ml (1.6 M, 55 mmole) of n-butyllithium (n-BuLi) was added into the solution under an ice bath. Themixture turned orange red. The ice bath was removed and the mixture wasstirred for 3 hours. 7.4 g of 6,6-hexamethylenefulvene (46 mmole) wasadded gradually to the mixture. After stirring for 24 hours, 1 ml ofwater was added to the mixture to terminate the reaction. The reactionmixture was stripped under vacuum to remove solvent, washed with 100 mlof pentane, and filtered to remove the salt. The crude product (i.e.,filtrate) was purified by column chromatography (the packing was 20 g ofsilica gel, the eluent was 100% pentane). The solution was thenconcentrated under reduced pressure to obtain a pale yellow liquid (8.6g, yield=67.7%).

(3)cycloheptylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)bis(dimethylamino)zirconium

1 g of 1-cyclopentadienyl-1-indenylcycloheptane (3.6 mmol) obtained andZr(NMe₂)₄ (0.86 g, 3.2 mmol) were placed in a 100 ml round bottle flask.50 ml of toluene was added to the flask and the mixture was allowed toreact for 24 hours. The reaction mixture was stripped under vacuum toremove solvent and then 20 ml of pentane was added to dissolve theresidue. The solution was filtered and the filtrate was thenconcentrated to obtain an orange yellow solid (1.25 g, yield=86%).

(4) cycloheptylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)-zirconiumdichloride

0.5 g ofcycloheptylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)bis(dimethylamino)zirconium(1.1 mmol) was charged in a 100 ml round bottle and 20 ml of toluene wasadded. 0.36 g of (CH₃)₃SiCl (3.3 mmol) was added gradually at roomtemperature and the mixture was allowed to react for 24 hours. Thereaction mixture stripped under vacuum to remove solvent and washed withpentane several times to remove excess (CH₃)₃SiCl. The pentane solutionwas then concentrated to obtain a pale yellow solid (0.41 g,yield=85.2%). X-ray crystal structure of the productcycloheptylidenel(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)-zirconiumdichloride is shown in FIG. 4. The bite angle of the product is 99.8°.

COMPARATIVE CATALYST EXAMPLE 9 Synthesis ofcyclohexylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)zirconium dichloride(Catalyst E)

(1) 6,6-pentamethylenefulvene

7 g of cyclohexanone (71 mmol) and 14.35 ml of cyclopentadiene(175 mmol)were charged in a 300 ml reaction bottle. 70 ml of CH₃OH was added as asolvent. Then, 8.75 ml of pyrrolidine (105 mmol) was added gradually andthe mixture was stirred at room temperature for 30 minutes. Next, 6.3 mlof CH₃COOH (105 mmol) was added gradually and stirred for 10 minutes.200 ml of H₂O and 200 ml of pentane were used for extraction. The upperpentane portion was collected. The lower water portion was furtherextracted with pentane three times. The collected pentane portion wasdehydrated with MgSO₄, held still for 30 minutes, filtered, andconcentrated under reduced pressure to afford a yellow liquid product(8.7 g, yield=83.3%).

(2) 1-cyclopentadienyl-1-indenylcyclohexane

Indene (5.8 g, 50 mmole) was placed in a 250 ml round bottom flask with50 ml of THF (tetrahydrofuran). 34.3 ml (1.6 M, 55 mmole) of n-butyllithium (n-BuLi) was added into the solution under an ice bath. Themixture turned orange red. The ice bath was removed and the mixture wasstirred for 3 hours. 6.7 g of 6,6-pentamethylenefulvene (46 mmole) wasadded gradually to the mixture. After stirring for 24 hours, 1 ml ofwater was added to the mixture to terminate the reaction. The reactionmixture was stripped under vacuum to remove solvent, washed with 100 mlof pentane, and filtered to remove the salt. The crude product (i.e.,filtrate) was purified by column chromatography (the packing was 20 g ofsilica gel, the eluent was 100% pentane). The solution was thenconcentrated under reduced pressure to obtain a pale yellow liquid (8.3g, yield=69%).

(3)cyclohexylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)bis(dimethylamino)zirconium

1 g of 1-cyclopentadienyl-1-indenylcyclohexane (3.8 mmol) obtained andZr(NMe₂)₄ (0.91 g 3.4 mmol) were placed in a 100 ml round bottle flask.50 ml of toluene was added to the flask and the mixture was allowed toreact for 24 hours. The reaction mixture was stripped under vacuum toremove solvent and then 20 ml of pentane was added to dissolve theresidue. The solution was filtered and the filtrate was thenconcentrated to obtain an orange yellow solid (1.27 g, yield=84.8%).

(4) cyclohexylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)-zirconiumdichloride

0.53 g ofcyclohexylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)bis(dimethylamino)zirconium(1.2 mmol) was charged in a 100 ml round bottle and 20 ml of toluene wasadded. 0.39 g of (CH₃)₃SiCl (3.6 mmol) was added gradually at roomtemperature and the mixture was allowed to react for 24 hours. Thereaction mixture stripped under vacuum to remove solvent and washed withpentane several times to remove excess (CH₃)₃SiCl. The pentane solutionwas then concentrated to obtain a pale yellow solid (0.42 g,yield=82.5%). X-ray crystal structure of the productcyclohexylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)-zirconiumdichloride is shown in FIG. 5. The bite angle of the product is 97.3°.

Polymer Synthesis EXAMPLE A Synthesis of Ethylene/Norbornene Copolymer

Toluene was refluxed in the presence of sodium to remove water to awater content of less than 10 ppm. 500 g of norbornene and 88 g of drytoluene were mixed under nitrogen to obtain an 85 wt % norbornenesolution.

A 500 ml reactor vessel was heated to 120° C., evacuated for 1 hour, andthen purged with nitrogen gas three or four times to ensure completeremoval of moisture and oxygen. Ethylene was introduced into the reactorto replace nitrogen and expelled. The procedure was repeated again.After this, 100 g of the 85 wt % norbornene solution was then charged inthe reactor under a nitrogen atmosphere and the solution was stirred ata rate of 250 rpm while 4 ml of 1.49 M MAO (methyl aluminoxane) wasinjected into the reactor by a syringe.

The reactor temperature was adjusted to 100° C. After the temperaturewas stabilized, 1 mg of the metallocene complex obtained as in CatalystExample 3 was dissolved in 1 ml of toluene in a glove box. Then, 3 ml ofMAO was added in the metallocene solution for activation. After fiveminutes of activation, the metallocene solution was then injected intothe reactor to initiate polymerization and the mixture was stirred at arate of 750 rpm. Finally, ethylene at a pressure of 15 kg/cm² wasintroduced into the reactor to a saturation level in the solution andthe stir rate for the mixture was maintained at 750 rpm. The reactionproceeded for 30 minutes.

After the completion of the polymerization reaction, the reactionsolution was poured into an acetone solution to precipitate the product.The product was washed with acetone two or three times, filtered, anddried in vacuum oven at 80° C. for 12 hours. The obtained copolymer was43.2 g. The results for this example are shown in Table 4.

EXAMPLES B to F

The same procedures as described in Example A were repeated to preparevarious cycloolefin copolymers except that the reaction temperature, themetallocene amount, and the MAO amount were changed. The metalloceneused in Examples A to F was the same. The results obtained are shown inTable 4.

TABLE 4 Metallocene Reaction ethylene Complex MAO Temperature pressureYield Activity Tg Example (mg) (ml) (° C.) (kg/cm²) (g) (g/gZr · hr) (°C.) A 1 7 100 15 43.2  3.9 × 10⁵ 173 B 0.24 1.3 80 15 10.9 2.07 × 10⁵163 C 0.23 1.3 100 15 15.3 5.90 × 10⁵ 176 D 0.22 1.3 120 15 20.4 8.23 ×10⁵ 185 E 0.23 1.3 140 15 26.4 10.2 × 10⁵ 195 F 0.24 1.3 155 15 11.14.22 × 10⁵ 193

COMPARATIVE EXAMPLE G (Compared with Example A)

Toluene was refluxed in the presence of sodium to remove water to awater content of less than 10 ppm. 500 g of norbornene and 88 g of drytoluene were mixed under nitrogen to obtain an 85 wt % norbornenesolution.

A 500 ml reactor vessel was heated to 120° C., evacuated for 1 hour, andthen purged with nitrogen gas three or four times to ensure completeremoval of moisture and oxygen. Ethylene was introduced into the reactorto replace nitrogen and expelled. The procedure was repeated again.After this, 100 g of the 85 wt % norbornene solution was then charged inthe reactor under a nitrogen atmosphere and the solution was stirred ata rate of 250 rpm while 4 ml of 1.49 M MAO (methyl aluminoxane) wasinjected into the reactor by a syringe.

The reactor temperature was adjusted to 100° C. After the temperaturewas stabilized, 1 mg ofdiphenylmethylidene(cyclopentadienyl)(9-fluorenyl) zirconium dichloridewas dissolved in 1 ml of toluene in a glove box. Then, 3 ml of MAO wasadded in the metallocene solution for activation. After five minutes ofactivation, the metallocene solution was then injected into the reactorto initiate polymerization and the mixture was stirred at a rate of 750rpm. Finally, ethylene at a pressure of 15 kg/cm² was introduced intothe reactor to a saturation level in the solution and the stir rate forthe mixture was maintained at 750 rpm. The reaction proceeded for 30minutes.

After the completion of the polymerization reaction, the reactionsolution was poured into an acetone solution to precipitate the product.The product was washed with acetone two or three times, filtered, anddried in vacuum oven at 80° C. for 12 hours. The obtained copolymer was26.9 g. The results obtained are shown in Table 5.

TABLE 5 Reaction Ethylene MAO (ml)/ Ex- Temperature Pressure 100 mlActivity Tg ample (° C.) (kg/cm²) 85% Nb g/gZr · hr (° C.) G 100 15 71.60 × 10⁶ 154 A 100 15 7 3.90 × 10⁶ 173 Nb = norbornene

EXAMPLES I to K

The same procedures as described in Example A were repeated to preparevarious cycloolefin copolymer having a high Tg except that the reactiontemperature was set to 120° C., the reaction time was lengthened to 1hour, the ethylene pressure was changed, and the amounts of metalloceneand MAO were changed. The metallocene used in Examples I to K was thesame as that used in Example A. The results obtained are shown in Table6.

TABLE 6 Metallocene Reaction ethylene Complex MAO Temperature pressureYield Activity Tg Example (mg) (ml) (° C.) (kg/cm²⁾ (g) (g/gZr · hr) (°C.) I 1.05 1.3 120 3 27.4 1.17 × 10⁵ 292 J 0.52 1.3 120 5 24.4 2.14 ×10⁵ 245 K 0.55 1.3 120 7 34.9 2.87 × 10⁵ 232

COMPARATIVE EXAMPLE L (Compared with Example J)

Toluene was refluxed in the presence of sodium to remove water to awater content of less than 10 ppm. 500 g of norbornene and 88 g of drytoluene were mixed under nitrogen to obtain an 85 wt % norbornenesolution.

A 500 ml reactor vessel was heated to 120° C., evacuated for 1 hour, andthen purged with nitrogen gas three or four times to ensure completeremoval of moisture and oxygen. Ethylene was introduced into the reactorto replace nitrogen and expelled. The procedure was repeated again.After this, 100 g of the 85 wt % norbornene solution was then charged inthe reactor under a nitrogen atmosphere and the solution was stirred ata rate of 250 rpm while 4 ml of 1.49 M MAO (methyl aluminoxane) wasinjected into the reactor by a syringe.

The reactor temperature was adjusted to 100° C. After the temperaturewas stabilized, 1 mg ofdiphenylmethylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloridewas dissolved in 1 ml of toluene in a glove box. Then, 3 ml of MAO wasadded in the metallocene solution for activation. After five minutes ofactivation, the metallocene solution was then injected into the reactorto initiate polymerization and the mixture was stirred at a rate of 750rpm. Finally, ethylene at a pressure of 15 kg/cm² was introduced intothe reactor to a saturation level in the solution and the stir rate forthe mixture was maintained at 750 rpm. The reaction proceeded for 30minutes.

After the completion of the polymerization reaction, the reactionsolution was poured into an acetone solution to precipitate the product.The product was washed with acetone two or three times, filtered, anddried in vacuum oven at 80° C. for 12 hours. The obtained copolymer was15.3 g. The results obtained are shown in Table 7.

TABLE 7 Metallocene Reaction ethylene Complex MAO Temperature pressureYield Activity Tg Example (mg) (ml) (° C.) (kg/cm²) (g) (g/gZr · hr) (°C.) J 0.52 1.3 120 5 24.4 2.14 × 10⁵ 245 L 1.00 7 120 5 15.3 9.37 × 10⁴199

EXAMPLES M to O

The same procedures as described in Example A were repeated to preparevarious cycloolefin copolymers except that the reaction temperature wasset to 120° C., ethylene pressure was changed, and the amounts ofmetallocene and MAO were changed. The metallocene used in Examples M toO was the same as that used in Example A. The results obtained are shownin Table 8.

TABLE 8 Metallocene Reaction ethylene Complex MAO Temperature pressureYield Activity Tg Example (mg) (ml) (° C.) (kg/cm³) (g) (g/gZr · hr) (°C.) M 0.22 1.3 120 15 20.4  8.23 × 10⁵ 185 N 0.49 3.4 120 30 59.0 10.9 ×10⁵ 147 O 0.47 3.4 120 60 52.5 10.0 × 10⁵ 105

EXAMPLES P to S

The same procedures as described in Example A were repeated to preparevarious cycloolefin copolymers except that the reaction temperature,ethylene pressure, and the amounts of metallocene and MAO were changed.The metallocene used in Examples P to S was the same as that used inExample A. The norbornene used had difference concentrations in theseexamples. The results obtained are shown in Table 9.

TABLE 9 Metallocene norbornene Reaction ethylene Complex MAOconcentration Temperature pressure Yield Activity Tg Example (mg) (ml)(%) (° C.) (kg/cm²) (g) (g/gZr · hr) (° C.) P 0.23 1.3 85 120 15 28.55.50 × 10⁵ 183 Q 0.22 1.3 50 120 15 30.8 12.4 × 10⁵ 156 R 0.46 5.2 85100 60 70.6 1.36 × 10⁵ 103 S 0.47 5.2 50 100 60 33.0 6.30 × 10⁵  66

EXAMPLE T

The same procedures as described in Example A were employed, except thatthe metallocene compound used was changed to that prepared from Example5, the reaction temperature was 120° C., the reaction time was 10minutes, and Al/Zr in mole was 3000. The results are shown in Table 10.

COMPARATIVE EXAMPLE U

The same procedures as described in Example T were employed, except thatthe metallocene compound used was changed to those used in U.S. Pat. No.5,559,199 (dimethyl silyl-(1-indenyl)-cyclopentadienyl zirconiumdichloride and U.S. Pat. No. 5,602,219 (isopropenylidenecyclopentadienyl fluorenyl)zirconium dichloride. The results are shownin Table 10.

TABLE 10 Ethylene Reaction Norbornene pressure time Yield Tg ActivityConversion Catalysts (kg/cm²) (min) (g) (° C.) g/g Zr · hr (%) USP5,559,199 15 10 4.8 89.66  3.9E+05 5.1 USP 5,602,219 15 10 23.6 159.961.92E+06 25.40 Catalyst 15 10 32.0 186.15 2.59E+06 36.29 prepared inCatalyst Example 5

It can be seen from Table 10 that compared with the conventionalcatalyst systems, using the catalyst composition of the presentinvention, the obtained cycloolefin copolymer has an increasednorbornene conversion and a substantially increased glass transitiontemperature (Tg), still maintaining high catalytic activity.

POLYMERIZATION EXAMPLE 1 Synthesis of Ethylene/Norbornene Copolymer

A 500 ml reactor vessel was purged with nitrogen three or four times.100 ml of a norbornene solution (85 wt % in toluene) was introduced intothe reactor vessel under nitrogen. The stirring rate was adjusted to 250rpm. Ethylene was introduced into the reactor to replace nitrogen andexpelled. The procedure was repeated three times. After this, 2 ml ofMAO (1.49 M) was injected into the reactor at 60° C. 0.012 of catalyst A[cyclobutylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)zirconiumdichloride] prepared from Catalyst Example 6 was dissolved in 10 ml oftoluene in a glove box and 0.4 ml of MAO (1.49 M) was added to 0.9 g ofthe catalyst solution (2.74×10⁻⁶ mol). After five minutes of activation,the catalyst solution (containing MAO) was then injected into thereactor. When the mixture was heated to the reaction temperature (100°C.), ethylene at a pressure of 1.0 kg/cm² was introduced into thereactor to start polymerization and the stir rate for the mixture wasmaintained at 750 rpm. The reaction proceeded for 30 minutes.

After the completion of the polymerization reaction, the reactionsolution was diluted with 100 ml of toluene and then poured into anacetone solution (containing diluted HF) to precipitate the product. Theproduct was washed with acetone two or three times, filtered, and driedin vacuum oven for 12 hours. The obtained copolymer was 26.3 g. Theresults for this example are shown in Table 11.

POLYMERIZATION EXAMPLES 2-3

The same procedures as described in Polymerization Example 1 wereemployed except that the metallocene catalysts used were changed toCatalyst B[cyclopentylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)zirconiumdichloride] (0.95 g, 2.74×10⁻⁶ mol) prepared from Catalyst Example 7 andCatalyst C[cycloheptylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)-zirconiumdichloride] (1.0 g, 2.74×10⁻⁶ mol) prepared from Comparative CatalystExample 8 respectively. The results are shown in Table 11.

COMPARATIVE POLYMERIZATION EXAMPLE 4

The same procedures as described in Polymerization Example 1 wereemployed except that the metallocene catalyst used was changed toCatalyst D [diphenylmethylidene(cyclopentadienyl)(9-fluorenyl)-zirconiumdichloride] (1.3 g, 2.74×10⁻⁶ mol). The results are shown in Table 11.

COMPARATIVE POLYMERIZATION EXAMPLE 5

The same procedures as described in Polymerization Example 1 wereemployed except that the metallocene catalyst used was changed to 0.97 g(2.74×10⁻⁶ mol) of Catalyst E obtained from Comparative Catalyst Example9 mol). The results are shown in Table 11.

TABLE 11 Catalyst (member number Polymerization of the Product ActivityTg Example bridging ring) (g) (g/gZr · hr) (° C.) 1 A (four members)26.3 2.1 × 10⁵ 289.1 2 B (five members) 26.3 2.1 × 10⁵ 288.3 3 C (sevenmembers) 21.5 1.7 × 10⁵ 285.8 4 D (no ring) 6.9 0.5 × 10⁵ 216.3 5 E (sixmembers) 15.7 1.3 × 10⁵ 288.3 A:cyclobutylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)zirconium dichlorideB: cyclopentylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)zirconiumdichloride C:cycloheptylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)zirconiumdichloride D:diphenylmethylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichlorideE: cyclohexylidene(1-η⁵-cyclopentadienyl)(1-η⁵-indenyl)zirconiumdichloride

POLYMERIZATION EXAMPLE 6

The same procedures as described in Polymerization Example 1 wereemployed except that the reaction temperature was changed to 120° C. andthe reaction pressure was changed to 1.5 kg/cm². The results are shownin Table 12.

POLYMERIZATION EXAMPLES 7-9

The same procedures as described in Polymerization Example 6 wereemployed except that the metallocene catalysts used were changed toCatalyst B (0.95 g, 2.74×10⁻⁶ mol), Catalyst C (1.0 g, 2.74×10⁻⁶ mol),and Catalsyt E (0.97 g, 2.74×10⁻⁶ mol) respectively. The results areshown in Table 12.

TABLE 12 Catalyst (member number Polymerization of the Product ActivityTg Example bridging ring) (g) (g/gZr · hr) (° C.) 6 A (four members)33.4 2.7 × 10⁵ 330.2 7 B (five members) 33.6 2.6 × 10⁵ 317.1 8 C (sevenmembers) 29.4 2.4 × 10⁵ 310.3 9 E (six members) 19.5 1.6 × 10⁵ 309.9

POLYMERIZATION EXAMPLE 10

The same procedures as described in Polymerization Example 6 wereemployed except that the reaction time was changed to 20 minutes. Theresults are shown in Table 13.

POLYMERIZATION EXAMPLES 11-13

The same procedures as described in Polymerization Example 10 wereemployed except that the metallocene catalysts used were changed toCatalyst B (0.95 g, 2.74×10⁻⁶ mol), Catalyst C (1.0 g, 2.74×10⁻⁶ mol),and Catalyst E (0.97 g, 2.74×10⁻⁶ mol) respectively. The results areshown in Table 13.

TABLE 13 Catalyst (member number Polymerization of the Product ActivityTg Example bridging ring) (g) (g/gZr · hr) (° C.) 10 A (four members)26.0 3.1 × 10⁵ 312.1 11 B (five members) 26.0 3.1 × 10⁵ 307.1 12 C(seven members) 25.7 3.1 × 10⁵ 305.7 13 B (six members) 14.6 1.7 × 10⁵310.3

Tables 11-13 compare the polymerization using the catalyst compositionof the present invention and the conventional one. The inventivecatalyst composition includes a metallocene bridged by a four- orfive-member ring. The conventional catalyst composition includes ametallocene bridged by a six- or seven-member ring, or bridged by acarbon with no ring. It can be seen from Tables 11-13 that compared withthe conventional catalyst systems, using the catalyst composition of thepresent invention, the obtained cycloolefin copolymer has an increasednorbornene conversion and a substantially increased glass transitiontemperature (Tg), still maintaining high catalytic activity.

The foregoing description of the preferred embodiments of this inventionhas been presented for purposes of illustration and description. Obviousmodifications or variations are possible in light of the above teaching.The embodiments chosen and described provide an excellent illustrationof the principles of this invention and its practical application tothereby enable those skilled in the art to utilize the invention invarious embodiments and with various modifications as are suited to theparticular use contemplated. All such modifications and variations arewithin the scope of the present invention as determined by the appendedclaims when interpreted in accordance with the breadth to which they arefairly, legally, and equitably entitled.

1. A process for preparing an olefin polymer, comprising the step of:polymerizing (a) an olefin, or (b) at least one olefin with at least oneother monomer, under polymerizing conditions in the presence of acatalytically effective amount of a catalyst composition comprising: (i)a metallocene compound represented by the following formula

wherein R is a C₁-C₂₀ hydrocarbyl group; and (ii) an activatingcocatalyst selected from the group consisting of (1) an aluminoxane, (2)a mixture of AlR¹¹R¹²R¹³ and a borate, or (3) a mixture of AlR¹¹R¹²R¹³and an aluminoxane, wherein R¹¹, R¹², and R¹³ are a C₁₋₂₀ aliphaticgroup or a C₆₋₁₀ aromatic group.
 2. A process for preparing an olefinpolymer, comprising the step of: polymerizing (a) an olefin, or (b) atleast one olefin with at least one other monomer, under polymerizingconditions in the presence of a catalytically effective amount of acatalyst composition comprising: (i) a metallocene compound representedby the following formula

wherein R is a C₁-C₂₀ hydrocarbyl group; and (ii) an activatingcocatalyst selected from the group consisting of (1) an aluminoxane, (2)a mixture of AlR¹¹R¹²R¹³ and a borate, or (3) a mixture of AlR¹¹R¹²R¹³and an aluminoxane, wherein R¹¹, R¹², and R¹³ are a C₁₋₂₀ aliphaticgroup or a C₆₋₁₀ aromatic group.
 3. A process for preparing an olefinpolymer, comprising the step of: polymerizing (a) an olefin, or (b) atleast one olefin with at least one other monomer, under polymerizingconditions in the presence of a catalytically effective amount of acatalyst composition comprising: (i) a metallocene compound representedby the following formula

wherein R is a C₁-C₂₀ hydrocarbyl group; and (ii) an activatingcocatalyst selected from the group consisting of (1) an aluminoxane, (2)a mixture of AlR¹¹R¹²R¹³ and a borate, or (3) a mixture of AlR¹¹R¹²R¹³and an aluminoxane, wherein R¹¹, R¹², and R¹³ are a C₁₋₂₀ aliphaticgroup or a C₆₋₁₀ aromatic group.
 4. A process for preparing an olefinpolymer, comprising the step of: polymerizing (a) an olefin, or (b) atleast one olefin with at least one other monomer, under polymerizingconditions in the presence of a catalytically effective amount of acatalyst composition comprising: (i) a metallocene compound representedby the following formula

wherein A is halogen; and (ii) an activating cocatalyst selected fromthe group consisting of (1) an aluminoxane, (2) a mixture of AlR¹¹R¹²R¹³and a borate, or (3) a mixture of AlR¹¹R¹²R¹³ and an aluminoxane,wherein R¹¹, R¹², and R¹³ are a C₁₋₂₀ aliphatic group or a C₆₋₁₀aromatic group.
 5. A process for preparing an olefin polymer, comprisingthe step of: polymerizing (a) an olefin, or (b) at least one olefin withat least one other monomer, under polymerizing conditions in thepresence of a catalytically effective amount of a catalyst compositioncomprising: (i) a metallocene compound represented by the followingformula

wherein R is a C₁-C₂₀ hydrocarbyl group; and (ii) an activatingcocatalyst selected from the group consisting of (1) an aluminoxane, (2)a mixture of AlR¹¹R¹²R¹³ and a borate, or (3) a mixture of AlR¹¹R¹²R¹³and an aluminoxane, wherein R¹¹, R¹², and R¹³ are a C₁₋₂₀ aliphaticgroup or a C₆₋₁₀ aromatic group.
 6. A process for preparing an olefinpolymer, comprising the step of: polymerizing (a) an olefin, or (b) atleast one olefin with at least one other monomer, under polymerizingconditions in the presence of a catalytically effective amount of acatalyst composition comprising: (i) a metallocene compound representedby the following formula

wherein A is a C₂-C₂₀ hydrocarbyl group; and (ii) an activatingcocatalyst selected from the group consisting of (1) an aluminoxane, (2)a mixture of AlR¹¹R¹²R¹³ and a borate, or (3) a mixture of AlR¹¹R¹²R¹³and an aluminoxane, wherein R¹¹, R¹², and R¹³ are a C₁₋₂₀ aliphaticgroup or a C₆₋₁₀ aromatic group.
 7. A process for preparing an olefinpolymer, comprising the step of: polymerizing (a) an olefin, or (b) atleast one olefin with at least one other monomer, under polymerizingconditions in the presence of a catalytically effective amount of acatalyst composition comprising: (i) a metallocene compound representedby the following formula

wherein A is halogen; and (ii) an activating cocatalyst selected fromthe group consisting of (1) an aluminoxane, (2) a mixture of AlR¹¹R¹²R¹³and a borate, or (3) a mixture of AlR¹¹R¹²R¹³ and an aluminoxane,wherein R¹¹, R¹², and R¹³ are a C₁₋₂₀ aliphatic group or a C₆₋₁₀aromatic group.
 8. A process for preparing an olefin polymer, comprisingthe step of: polymerizing (a) an olefin, or (b) at least one olefin withat least one other monomer, under polymerizing conditions in thepresence of a catalytically effective amount of a catalyst compositioncomprising: (i) a metallocene compound represented by the followingformula

wherein A is halogen; and (ii) an activating cocatalyst selected fromthe group consisting of (1) an aluminoxane, (2) a mixture of AlR¹¹R¹²R¹³and a borate, or (3) a mixture of AlR¹¹R¹²R¹³ and an aluminoxane,wherein R¹¹, R¹², and R¹³ are a C₁₋₂₀ aliphatic group or a C₆₋₁₀aromatic group.